Tandem Silylformylation-Crotylsilylation/Tamao Oxidation of Internal Alkynes: A Remarkable Example of Generating Complexity from Simplicity
Tandem Silylformylation-Crotylsilylation/Tamao Oxidation of Internal Alkynes: A Remarkable Example of Generating Complexity from Simplicity
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DOI：
10.1021/ol802489w
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发表时间：
2008-12-18
期刊：
影响因子：
5.2
通讯作者：
Leighton, James L.
中科院分区：
文献类型：
--
作者：
Spletstoser, Jared T.;Zacuto, Michael J.;Leighton, James L.
Rh催化的串联硅甲酰化-巴豆基硅基化反应已扩展到包括内炔。初始产物的Tamao氧化导致取代烯醇的产生，该取代烯醇经历高度非对映选择性的互变异构化。由此产生的一锅法形成了三个新的立体中心，一个酮和一个端烯，来自丁烯基、丙炔基、硅氢化物、H_2O_2和CO。
The rhodium-catalyzed tandem silylformylation-crotylsilylation reaction has been extended to include internal alkynes. Tamao oxidation of the initial product leads to the production of a substituted enol, which undergoes highly diastereoselective tautomerization. The resulting one-pot procedure fashions three new stereocenters, a ketone, and a terminal alkene from a butenyl group, a propynyl group, a silyl hydride, H2O2, and CO.